Amino-substituted dicyanoethylenes



United States Patent" ANHNO-SUBSTITUTED DICYANOETHYLENES William J. Middleton, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 30,1954

, Serial No. 453,143

Claims. (Cl. 26078.4)

This invention relates to novel chemical compounds and their preparation, particularly aminosubstituted dicyanoethylenes and production of them from dicyanoketene acetals.

Dicyanoketene acetals may be characterized by the formula (NC) C=C( OR) where each R signifies a hydrocarbon radical linked to oxygen and perhaps linked to the other R as well, being monovalent in the first instance and divalent in the second. This structure conveniently may be represented more generally as follows:

the. dotted line indicating the optional bond between hydrocarbon radicals R and R, which may be alike or unlike. Copending patent application of Heckert and Middleton, Serial No. 416,720, filed March 16, 1954, now abandoned (also Middleton et al., I. Am. Chem. Soc. 80, 2788 (1958-) describes preparation of dicyanoketene acetals in the presence of a catalyst (such as urea, metal salt, or tertiary amine) from alcohols and tetracyanoethylcue, the latter of which may be formed by reaction of sulfur monochloride and malononitrile as described'in Cairns et al. J. Am. Chem. Soc. 80, 2775 (1958). The hetero.- cyclic dicyanoketene. acetals (i.e.,. 2-dicyanomethylene-l,3- dioxacycloaliphatic compounds) suggested. above result when dihydric alcohols are reacted with tetracyanoethylene according to Heckert and Middleton.

The primary objeet of the present invention is preparation of amino-substituted dicyanoethylenes. Another object is provision of new compounds of this class. Other objects will be apparent from the following description of the invention.

In general, the objects of the present invention are accomplished 'by reaction of at least one equivalent of ammonia or primary or secondary amine with dicyanoketene acetals; thus, a compound as formulated above is reacted with: a. compound containing one or more amino groups having. replaceablev hydrogen, and at least one of the carbon-to-oxygen bonds of the acetal breaks and the bond from one replaceable hydrogen to the amino nitrogen breaks, whereupon these carbon and nitrogen atoms link together in the product. The invention comprehends products in which both, as well as those in which only one, of the; starting acetal groups are replaced by amino groups; along with aliphatic monomeric compounds, these include polymeric compounds and cyclic monomers.

When an amine being reacted with the dicyanoketene acetal contains more than one primary or secondary amino group per' molecule, both acetal groups normally are replaced thereby, giving a hcterocyclic product when the amino groups are located close to one another in the molecule or giving a polymeric product when the amino groups are separated considerably from one another in the molecule. When the reactant molecule contains only one amino group having replaceable hydrogen, a product in which only one acetal group is replaced by amine normally is recoverable. In the latter instance, the remaining acetal group is unaffectedwhen the original molecule contained two separate acetal groups; however, when the original molecule had the acetal groups linked carbon-tocarbon with one another to form a dicyanomethyl -substituted dioxa-alicyclic compound, reaction with one amine equivalent leaves the combined hydrocarbon residue attached to the unaffected oxygen, but in hydroxy-substituted form (a 1-amino-2,2-dicyanovinyl hydroxyaliphatic ether). The process of this invention contemplates reaction ofstarti'ng dicyanoketene acetal produced in situ from the starting materials of Heckert and Middleton, mentioned above, the same result being obtained as if the compound existed separately. The following examples, in which parts and percentages are byweight unless otherwise indicated, illustrate the practice of this invention.

EXAMPLE I No o-om No NH.

o=o +2vn3v o=o +(CHzOH); NC/ OCH: No NH.

A mixture of 136 parts of dicyanoketene ethylene acetal and 450 parts of concentrated ammonium hydroxide (28.3% NH by weight) is heated under reflux for 10 minutes, and then allowed to stand overnight. The white crystalline plates which form are collected on a filter, washed with water, and recrystallized from water. There is obtained 100 parts (93%) of 1,l-diamino-2,2-dicyanoethylene in the" form of: white needles, M.P. 236-238 0 X-ray difiraction patterns of. the crude plates and the recrystallized needles are identical.

Analysis.-Calcd. for C H N C, 44.44; H, 3.73; N, 51.82. Found: C, 44.34; H, 3.86; N, 51.67, 51.52.

Spectral. analysis indicates that 1,1-diamino-2,2-dicyanoethylene exists as, a. tetrasubstituted ethylene, and not as its tautomer, dicyanoacetamidine. A strong ultraviolet absorption maximum at 2510 A. indicates a high degree of resonance. The very characteristic NH bands at. 6.04 microns, 3.03 microns and 3.15 microns are observed in the infrared absorptionspectrum. A band at 6.43 microns which is very similar to the absorption band for C,=C in. the dicyanoketene acetals is also observed. Absence of CH bond absorption bands in the spectrum also indicates that the tautomeric dicyanoacetamidine is not present.

1,1-diamino-2,2-dicyanoethylene may be hydrolyzed in aqueous alkali as follows:

Ten parts of l,1-diamino 2,Z-dicyanoethylene is dissolved in 100 parts of hot 10% sodium hydroxide, the solutionis boiled for 5 minutes, and then cooled. A white precipitate forms, which is recrystallized from water. There-is obtained 7 parts (60%) of l,1-diamino-2-cyano- Z-carbamylethylene in the form of long white needles, M.P. 204205 C.

Aazalysia-Calcd. for C H N O:v C, 38.09; H, 4.80; N, 44.43. Found: C, 38.44, 38.52; H, 4.74, 4.88; N, 44168, 44.80.

EXAMPLE II Part A A mixture of 565 parts of dicyanoketene. diethyl acetal, 3000 parts of water and parts of an aqueous solution containing 119.17 parts of ammonium hydroxide is heated to boiling. The white crystalline solid which separates upon cooling is collected on a filter, washed with water and recrystallized from ethanol. There is'ob- 3 tained 310 parts (67%) of 1-amino-2,2-dicyanovinyl ethyl ether in the form of white needles, M.P. 225- 226 C.

Analysis.-Calcd. for CHqN O C, 52.54; H, 5.15; N, 30.64. Found: C, 52.84; H, 5.20; N, 30.65.

The ultraviolet absorption spectrum of 1-amino-2,2- dicyanovinyl ethyl ether shows a strong maximum absorption at 2540 A., which indicates a high degree of conjugation for such a small molecule. There is a doublet at 3.05 and 3.19 microns in the infrared ab sorption spectrum due to the NH; bonds. There is also a very strong and sharp band at 6.05 microns which is ,probably associated with the NH group, and a band at 6.48 microns which is very similar to the absorption band for C=C in dicyanoketene dimethyl acetal.

Alternative procedure for Part A A mixture of 64 parts of tetracyanoethylene, 30 parts of urea, and 395 parts of ethyl alcohol is heated until the purple color which first forms had faded to yellow. Concentrated ammonium hydroxide, 225 parts, and 750 parts of water are added to the warm solution and heating is continued for minutes. The light brown precipitate which forms upon cooling is collected on a filter,

washed with water and recrystallized from water containing dccolorizing carbon. There is obtained parts (22%) of 1-amino-2,2-dicyanovinyl ethyl ether in the form of white needles, M.P. 225-226 C.

Analysis.Calcd. for C H N O C, 52.54; H, 5.15; N, 30.64. Found: C, 52.68, 52.53; H, 5.17, 5.19; N,

Part B A mixture of 166 parts of dicyanoketene diethyl acetal and 900 parts of concentrated ammonium hydroxide (28.3% NH, by weight) is heated under reflux for 2.5 hours. The white solid which precipitates upon cooling is recrystallized from water to give 87 parts (81%) of 1,1-diamino-2,2-dicyanoethylene in the form of white needles, M.P. 234236 C. The infrared absorption spectrum of this compound is identical with that of the compound prepared from dicyanoketene ethylene acetal and ammonia as shown in Example 1.

EXAMPLE IV A mixture of 136 parts of dicyanoketene ethylene acetal and 200 parts of an aqueous solution containing methylamine is heated at its boiling temperature until all of the solid has dissolved. The precipitate which forms upon cooling is collected on a filter, washed with water and recrystallized from a very small amount of water. There is obtained 40 parts of 1,1- bis(methylamino)-2,2-dicyanoethylene in the form of white needles, M.P. 160-163 C.

Analysis.Calcd. for C H N C, 52.93; H, 5.92; N, 41.15. Found: C, 53.08, 53.27; H, 6.05, 5.95; N, 41.39, 41.29.

The infrared absorption spectrum contains a NH band at 3.0 microns.

EXAMPLE V Part A v mixture of 525 parts of dicyanoketene diethyl acetal,

2000 parts of water and 420 parts of an aqueous solution containing 98.15 parts of methylamine is heated until solution is complete. Upon cooling, a white crystalline mass separates. This material is collected on a filter, washed with water and recrystallized from water. There is obtained 350 parts (86%) of 1-methylamino-2,2- dicyanovinyl ethyl ether in the form of white plates, M.P. 98-99" C. This compound is slightly acidic as shown by the fact it dissolves in a sodium hydroxide solution but not in a sodium bicarbonate solution.

Analysis.Calcd. for C H ON C, 55.62; H, 6.00; N, 27.80. Found: C, 55.56, 55.21; H, 6.20, 6.11; N, 27.74, 27.67.

The infrared absorption spectrum of this compound indicates an NH band at 3.05 microns.

Part B A solution of 75 parts of 1-methylamino-2,2- dicyanovinyl ethyl ether in 900 parts of concentrated ammonium hydroxide is heated under reflux for 10 minutes. The solution is cooled, and a white solid precipitates. The solid is collected on a filter, washed with water and recrystallized from water. There is obtained 51 parts (84%) of l-amino-l-methylamino-2,2-dicyanoethylene in the form of white crystals, M.P. 198-200 C.

Analysis.Calcd. for C H N C, 49.17; H, 4.95; N, 45.88. Found: C, 49.18, 49.38; H, 4.99, 5.04; N, 45.60, 45.26.

EXAMPLE VI A solution of 136 parts of dicyanoketene ethylene acetal in 1360 parts of dimethylamine is allowed to evaporate overnight at room temperature. The residue is dissolved in 1000 parts of hot water and heated on a steam bath for 10 minutes. The White needles which form upon cooling are collected on a filter, washed with water and recrystallized from water. There is obtained parts (52%) of 1,1-bis(dimethylamino)-2,2-dicyanoethylene in the form of long white needles, M.P. 129- 130 C.

Analysis.-Calcd. for C H N C, 58.51; H, 7.37; N, 34.12. Found: C, 58.55, 58.38; H, 7.21, 7.35; N, 34.06, 34.23.

There are no bands due to NH or NH present in the infrared absorption spectrum. A band at 6.55 microns indicates the presence of a 0:0 bond.

EXAMPLE VII Ethylenediamine, parts, is added slowly to a solution of 272 parts of dicyauoketene ethylene acetal in 2220 parts of tetrahydrofuran. The mixture becomes warm, and a light yellow precipitate forms. This precipitate is collected on a filter, washed with tetrahydrofuran and then recrystallized from water. There is obtained 210 parts (79%) of Z-(dicyanomethylene)-imidazolidine in the form of white prisms, M.P. 279-280 C.

Analysis.-Calcd. for C H N C, 53.72; H, 4.51; N, 41.77; M.W., 134. Found: C, 54.01; H, 4.51; N, 41.65, 41.62; M.W. 144, 145.

Z-(dicyanomethylene) -imidazolidine may be hydrolyzed in aqueous caustic as follows. A mixture of 20 parts of 2-(dicyanomethy1ene)-imidazolidine and 200 parts of 10% aqueous sodium hydroxide is heated under reflux for one hour. All of the solid dissolves. The white precipitate which forms upon cooling is collected on a filter, washed with water and recrystallized from 200 parts of 10% sodium hydroxide solution. There is obtained 16 parts of 2-(carbamylcyanomethylene)-imidazolidine in the form of long white needles, M.P. 241-243 C.

Analysis.Calcd. for C H N O: C, 47.36; H, 5.30; N, 36.83. Found: C, 47.39, 47.47; H, 5.15, 5.43; N, 36.84, 36.97.

EXAMPLE VIII A mixture of 128 parts of tetracyanoethylene, 528 parts of trimethylene glycol and 10 parts of urea is heated until. all of the solid is dissolved. The solution is cooled, andfiflcparts ofiethylenediamine is added slowly. The reaction mixtureis mixed with 500 parts of water, and the light tan; precipitate which forms is collected on a filter and washed with water. The product is recrystali lized from dimethylformamide-water to give 95 parts (70% )1 of Z-(dicyanomet-hyIene)-imidazp1idine in the .form ofta crystalline white powder, M.P. 27 3 -274 C.

. Analysie-Calcd. for C H N C, 53.72; H, 4.51; N,

41.77 Found: C, 54.08; H, 4.64; N, 41.99, 42.1.0. 10

line solid which separates upon cooling is collected on a filter, washed with water and recrystallized from water. There is obtained 90 parts (60%) of l-amino-l-(Z-hydroxyethoxy)-2,2-dicyanoethylene (l-amino-2,2-dicyanovinyl 2-hydroxyethyl ether) in the form of white needles,

M.P. 164-165 .C.

Ahiz'lysis.-Calcd. for c n N o c, 47.05; H, 4.61; N, 27.44. Found: C, 47.34, 46.73; H, 4.89, 4.69; N, 27.25, 27.58.

acetal and parts of concentrated ammonium hydoxide :is heated untilaall of the solid has dissolved. The white crystalline solid which forms upon cooling is collected on a filter, washed with water and recrystallized from water. There is obtained 11, parts (66%) of 1-amino-l-(3-hydroxypropox-y) -'2,2.-dicyanoethylene (1-amino-2,2-dicyanovinyl 3-hydroxypropyl ether) in the form of ,white plates, M.P. 166-167 C.

Analysis.-Ca1cd. for C7H9N3O2I C, 50.29; H, 5.43; N, 25.14. Found: C, 50.17, 50.30; .H, 5.52, 5.58.; N, 25.1.0, 25.01.

EXAMPLE M A solution of 186 parts of dicyanoketene ethylene acetaland 159 parts of hexamethylenediamine in 888 parts of tetrahydrofuran is allowed to stand at room temperature for 18 hours. The tough, rubbery polymer which separates out is washed with hot water and dried. The polymer is not tacky and is insoluble in organic solvents; it consists predominantly of poly[(dicyanomethylene)-methazihexazamer], indicated by the following structural formula:

The 1-amino-2,2-dicyanovinyl ethers indicated below in Table I are obtained when the starting materials shown EXAMPLEX are reacted according to the first part of Examples 11 A mixture of 15 parts of dicyanoketene trimethylene or V or according to Example IX or Example X.

' TABLE I Starting materials Product Run Q 1-amino-2,2-dieyanovinyl ether Dlcyanoketene acetal Amine (1 equivalent) NC O-CH NC\ /.N A H-N =C\ NO OCH: NC '0CH;-CH1OH dlcyanoketene ethylene aeetal piperidlne 1-(2-hydroxyethoxy)-1-piperidino-2,2-dicyanoethylene- [2-d1cyanomethy1ene-1,3-dioxolane] [1-piperidino-2,2-dicyanoviny1 Z-hydroxyethyl ether] NC\ 0-o NC NH(CH2)u-CH: B /C=C\ C(C'Hah 2 i( :)i1 s /C=C\ NO 0-0 a No o-cm-cmmn-omon dicyanoketene 2,2-dimethy1- octadecylamtne 1-(2,2-dimethyl-3-hydroxypropoxy)-1-oetadecyl-amlno-2,Z-dieyanotrimethylene' acetal et; yene [2-dicyanomethylene-5 5- ll-octadeeylamlno-2,2-dieyanovinyl'2,2-dimethyl-3-hydroxypropyl dhnethyl-lB-dioxanel tether] I NC\ OCH("CH2)2C.H: NC\ N(C,Hm O /C=O\ H'N(CHo)1 /C==C\ NC O-=OH(CH2)r-CH|1 NO OCHCHOH 1) 1 1) dieyanoketene 1-2,dlpropy1-ethy1ene dlbutylamine 1-(1,2-dlpropyl-2-hydroxyethoxy-l-dibutylamino-z2-dieyanoethylene ac a1 [1-dibutylamino-2,2-dicyanovinyl 1,2-dipropy1-2-hydroxyethy] ether] [2-dicyanomethylene-4,5-

dipropyl-1,3-dioxolane] H 2 N0 NH CH r NC 0-CH 0H Y I D 0:0 HzN-CH:-

I V N0 0-011-011-011 N0 O- H CH CH, CH1

. CH=CH dioyanoketene 1,2-(4- henzylamine 1-.benzylamino-2,2-dicyanovinyl fi-hydroxy-Seyelohexenyl ether eyelohexene) ylene acetal [3,4-(dicyanomethy1ene)- -unethylenedioxyvleeyclo-hexenel NC OCH,CH=OH: NC NH-CH:CH,OH

' o=c 'mmonmon o=o Y F t NC O--CHCH=CH1 N61 .OCH:--CH=CH3 dieyanoketene diallyl aeetal Y ethano'lamlne l-fi-hydroxyethylamino-1-allyloxy-2,z-dieyano-ethylene I t[1-fl-hydr0xyethylamlno-2,Z-dieyanovinyl allyl ether] 7 "The." 1,l-diarmino-2,2-dicyanoethylenes indicated as productsin Table II are obtained by the reaction of a dicyanoketene acetal with two equivalents of an amine as in the processes of Examples I, III, -IV,VI, VII- and 8 at their normal melting temperaturesy which for many of them are substantially above 200 C. Thus,aalthough 1,2-diamino-l,2-dicyanoethylene decomposes 'at its'melting point of about 180 C. .-.(vL 'Woodward Patent VIII, or by the two-stepprocess of reactionof a dicy- 5 2,449,441), 1,1-diamino-2,2-dicyanoethylene is stable up anoketeneacetal: withsuccessive single equivalents of to and even above 235" C. I rtwo different amines as in the process methods of Exam- The above exemplification of this invention shows that ples II and V. .7 the required chemical reactions take place under mild,

' TABLE II 1 Run Dicyanoketene aeetal Amine (or amines) 1,1 dlamlno-2,2-dlcyanoethylene 0-011, 1: NC NH(GH,)11CH,' .A I c'= mmdnnuom c=o NC H'. No Nmouanom dicyanoketene dimethyl oetadecylamine v I 1,1-bis(octadecylamino)-2,2-dicyanoethylene acatal H No o-clrr. f NC I i-CH, B c=c Y (olmmmomnum o=o cm NC 0-Cz H5 NC NC 7 i l I T, 62H dicyanoketene diethyl acetal N -ethyltrlmethylenediamiue 1 -ethyl-2-(dlcyauomethylene)hexahydropyrlmldine H v v N Om NC\b.=/?CH2 I Eg I ,C-\ c= l g, e CH1 CH2 OH: H; NC 0-OH, NC N it dicyanoketene ethylene acetal piperazine 1,4-dilfigiigdgggalfiggggygfigfgfigfilgggigfiptane NC 0-011; HzNCHa-CH=OH: NC NHCHr-CH=CH: D"..- C=C CH1 allylamine C=0 OHPCH,

NC 0-Cz OKs-41H: NC/ \-NHC H1NC CHr-CH:

CHz-CH: v i dlcyanoketglclgtgliimethylene eyclopentylamine 1-a1lylamiuo-l-eyelopentylamlno-2,2-dleyanoethyleue H NC o-cm NC l t-0H, E-. I O=C HzN- CH:OH(UH;)OHNH2OH O=C CHI-0H;

NC 0CH| NC N0 -43H:

1'1 dicyanokgtcgrggldlmethyl 1,3-diamino-2-methylbutane 2-dieyauomethylene-4,S-dimethylhexahydropyrlmldine H v NC 0-CH: NC I I-CH.- F.. C=C H2NCHz-CH(CaH5)--CHNH1CHz(CeHs) C=C CHI-(Cell NC 0-0111 NC N -C OH:(C|H

dicyanoketene ethylene acetal 1,3-diamino-2,4-dlphenylbutane 4-benzyl-2-dicyanorii)gtlglfdzfig phenylhexahydro- The 1,1-diamino-2,2-dicyanoethylenes of the present invention differ sharply from known 1,2-diamino-1,2-dicyanoethylenes with which they are isomeric. For example, l,1-diamino-Z,Z-dicyanoethylene itself is neutral, exhibiting pH of about 7 in aqueous solution; whereas the isomeric tetramer of hydrogen cyanide variously described as 1,Z-diamino-1,2-dicyanoethylerre or 1,2-dicyano-l-amino-Z-iminoethane (or an equilibrium mixture of these two) is monobasic, forming a stable monohydrochloride that can be isolated readily (Hinkel, Y

Richards and Thomas, J. Chem. Soc. 1937, 1436). A

further distinction of these products is their increased thermal stability as compared with that of known isomers. The 1,1-diamino-2,2-dicyanoethylenes are thermally stable easily obtainable conditions. Ordinary room temperature usually sufiices, as does atmospheric pressure. Pressure above or below atmospheric may be employed without hindering the reaction; the rate of reaction normally increases with increasing temperature, which may be provided through external heating or may result from heat of reaction, and temperatures up to C. or so are economically useful in speeding the'reaction. Presence of water (v. Examples I to V, inclusive) is acceptable and convenient during-the reaction; an organic solvent may be used, instead (v. Examples VII and XI); or the reaction may be carried out in the absence of added liquid (v. Example VI). Except where the dicyanoketene acct-a1 is formed in situ, no catalyst is required.

--ableiproducts, as suggested in Table II. When-only one aceta'l {group has reacted, the larized generally as follows:

product may be formuwhere X stands for either a divalent hydrocarbon radical or for a pair of monovalent radicals each of which is either hydrogen or a hydrocarbon radical (i.e., two hydrogens, two monovalent hydrocarbon radicals, or one hydrogen and one monovalent hydrocarbon radical, both "attached to the nitrogen); and Q stands for either the original hydrocarbon radical of the acetal in that posi- -tion or for a hydroxy-substituted aliphatic hydrocarbon radical made up of adivalent hydrocarbon radical originally connected to :both oxygens, i.e., R-R'-OH. However, where the amine reactant is at .least difunctional, this intermediate product usually is not. isolated; instead, removal of both acetal groups gives either a monomeric product of relatively low molecular weight or a polymeric product of relatively 'high molecular weight. A monomer results when the second reactant is a diamine of formula:

Kayla where Y is a divalent hydrocarbon radical containing a chain of as many as three carbon atoms, and R" and .R''' when linked together constitute a divalent hydrocarbon radical and when separate from one another "constitute individual hydrogen or monovalent hydrocarbon radicals; a polymer results when the second reactant is a diamine of formula:

which difiers from the above diamine only by having Y (instead of Y) a divalent hydrocarbon radical containing a chain -of at least four carbon atoms. The monomer may be formularized generally (v. Table .II: B, C, E,

and 'F) as follows:

and the polymer '(v. Example XI) as follows:

I v ino ken longer diamines (e.g., hexamethylene, decamethylene,

dodecamethylene) have generally higher melting points and are tough and pliable; when coated onto cloth, as by a calender, they adapt it to use in upholstery materials characterized by increased stain resistance and other desirable properties. Many-of the products of this in vention are highly useful aschemica'l intermediates; for

i 10 example, aqueous caustic converts 1,1-diamino-2,2-dicyano'ethylen'es to corresponding 1,1-diamino-2-carbamyl- -2-cyanoethylenesi (Examples I and VII), which are known to be useful for removing metal ions from solution as chelates: cupric ion forming green chelates with 1,1 diamino 2 cyano .Z-carbamylethylene (Example I)-ferric ion instead forming therewith a deep red-brown chelate-and with 2-'(carbamylcyanomethylene) -irnidazolidine (Example VII) of the following respective prob- 'ketene acetal of the formula NC/ O1 t in which R and R when linked to one another constitute a divalent aliphatic hydrocarbon :group having from 2 to 3 carbon atoms in the hydrocarbon chain and not more 'than a total of 6 carbon atoms substituted on said chain and when separate from one another constitute individual monovalent aliphatic hydrocarbon radicals of the group consisting of lower alkyl and allyl, with a nitrogen-containing compound selected from the group consisting of ammonia, primary and secondary monoamines having from 1 to 18 carbon atoms and primary and secondary diamines having from .1 to v16 carbon atoms, whereby at least one of the carbon to oxygen bonds of the acetal is broken and replaced by a single bond from the same carbon to amino nitrogen of the nitrogen-containing compound at the expense of a hydrogen-to-nitrogen bond in said nitrogen-containing compound.

.2. The process which comprises treating a dicyanoketene acetal of the formula in which R and R when linked to one another constitute a divalent aliphatic hydrocarbon radical having from 2 to 3 carbon atoms in the hydrocarbon chain and not more than a total of .6 carbon atoms substituted on said chain and when separate from one :another constitute individual monovalent aliphatic hydrocarbon radicals-of the group consisting of lower alkyl and allyl, with an amine of the formula H1 I-Y-1iTH wherein Y constitutes a divalent hydrocarbon radical containing a chain of from 1 to 3 carbon atoms and R" and R' when linked to one another constitute a divalent aliphatichydrocarbon radical of the group consisting of lower alkyflene and substituted lower alkylene, the substituents on said substituted lowera'lkylene being of the group consisting of lower alkyl, phenyl and benzyl radicals, andR" and R" when separate'from 'one another acarbon radicals having from 1 to 18 carbon atoms, to produce a cyclic compound of the formula 3.' The process which comprises treating a dicyanoketene acetal of the formula Nc\ /O-R' it NC -H in which Rand R when linked to one another constitute a divalent aliphatic hydrocarbon radical having from 2 to 3 carbon atoms in the hydrocarbon chain and not more than a total of 6 carbon atoms substituted on said chain and when separate from one another constitute individual monovalentaliphatic hydrocarbon radicals of the group consisting of lower alkyl and allyl, with an equal molecu lar portion of an amine of the formula I 1 wherein Y constitutes a divalent hydrocarbon radical containing a chain of at least 4 carbon atoms and R" and R' constitute individual monovalent radicals from the group consisting of hydrogen and hydrocarbon radicals having from 1 to 18 carbon atoms, to produce a polymeric compound containing a recurring divalent unit of the formula in which -RR-- is a'divalent' aliphatic hydrocarbon carbon atoms substituted on said chain, with an equimo- 'lccular proportion of an amine of the formula HN=X,

wherein X is selected from the class consisting of lower alkylene radicals, substituted lower alkylene radicals, the substituents on said substituted lower alkylene radicals being members of the group consisting of lower alkyl, phenyl and benzyl, and pairs of separate monovalent radicals of the group consisting of hydrogen and hydrocarbon radicals having from-1 to 18 carbon atoms, to produce a compound of the formula I NC N x o '.o 0R-R'0H '5. The process which comprises treating a dicyanoketene acetal of the formula in which R and R are monovalent aliphatic hydrocarbon radicals'of the group consisting of lower alkyl and allyl, with an equimolecu'lar proportion of a nitrogen-containing compound of the formula HN =X wherein the X substituent is selected from the class consisting of lower alkylene radicals, substituted lower alkylene radicals in which the substituent groups are members of the class consisting of lower alkyl, phenyl and benzyl, and pairs of separate '45 radical having from 2 to 3 carbon atoms in the hydrocarbon chain and containing a total of not more than 6 monovalent radicals of the group consisting of hydrogen and hydrocarbon radicals of from, 1 to 18 carbon atoms, to produce a compound of the formula t NC 0.R 6. The process which comprises treating a'1-amino-2,2- dicyanovinyl ether selected from the group consisting of compounds of the formula where R is a monovalent aliphatic hydrocarbon radical of the group consisting of lower alkyl and allyl radicals and RR' is a divalent aliphatic hydrocarbon radical having from 2 to 3 carbon atoms in the hydrocarbon chain and containing not more than a total of 6 carbon atoms substituted on said chain, with an equirnolecular proportion of a nitrogen-containing compound of the formula HN='Z to produce a compound of the formula where Y constitutes a-divalent hydrocarbon radical containing a chain of from 1 to 3 carbon atoms and R" and R" when linked to one another constitute a divalent aliphatic hydrocarbon radical of the group consisting of lower alkylene and substituted lower alkylene radicals the substituents on the substituted alkylene group being members of the class consisting of lower alkyl, phenyl and benzyl radicals, and when separate from one another R" and R'" constitute individual monovalent radicals of the class consisting of hydrogen and hydrocarbon radicals having from 1 to 18 carbon atoms.

8. A polymeric compound containing a recurring divalent unit of the formula wherein Y constitutes a divalent hydrocarbon radical containing a chain of at least 4 carbon atoms, and R and R constitute individual monovalent radicals selected from the group consistingof hydrogen and hydrocarbon radicals having from 1 to 18 carbon atoms.

9. A: compound of the formula inwhich R R'- is a divalent aliphatic hydrocarbon 13 radical having from 2 to 3 carbon atoms in the hydrocarbon chain and not more than 6 carbon atoms substituted on said chain and X is selected from the class consisting of lower alkylene, substituted lower alkylene wherein the substituents thereon are selected from the group consisting of lower alkyl, phenyl and benzyl, and pairs of separate monovalent radicals of the group consisting of hydrogen and monovalent hydrocarbon radicals having from 1 to 18 carbon atoms.

10. A compound of the formula wherein X and Z are selected from the class consisting of lower alkylene, substituted lower alkylene in which the substituents are members of the class consisting of lower alkyl, phenyl and benzyl, and pairs of separate monovalent radicals from the group consisting of hydrogen and hydrocarbon radicals of from 1 to 18 carbon atoms.

References Cited in the file of this patent OTHER REFERENCES Linstead: J. Chem. Soc., 1937, page 920.

UNiTED STATES PATENT OFFICE Certificate of Correction Patent No. 2,883,368 April 21, 1959 William J. Middleton It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 19 to 22, Example I, for the first reactant in equation reading:

NO\ c-cH, NG\ /0-CHI read NC/ o- :m NC/ \O-CH1 column 2, line 68, Example II, for 80 parts read -800 parts; column 8, line 5, for the patent number 2,449,441 read 2,499,441-; columns 7 and 8, Table II, second column thereof, under the heading Amine (or amines), opposite Run B, for

(C HQN H (CH NH read -(C H )NH(CH NH column 9, lines 49 to 52, for the formula reading:

NC NR NC N-R" o=o i z I r ad o=o i'r 1 NO/ hi l-iv" NC/ \r-i'w column 11, line 45, for RPR read --RR'-; column 12, line 39, for radicals the read -radicals of the.

Signed and sealed this 25th day of August 1959.

[SEAL] Attest KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofiicer. Gonwm'ssz'oner of Patents. 

8. A POLYMERIC COMPOUND CONTAINING A RECURRING DIVALENT UNIT OF THE FORMULA 